Total synthesis of (+)-4-hydroxy-N-methylmorphinan-6-one and its O-methyl ether has been accomplished. The structure of the by-products obtained during the O-alkylation of (+)-2,4-dihydroxy-N-formylmorphinan-6-one with 1-chloro-5-phenyl-1H-tetrazole was established. An improved synthesis of this series of ketomorphinans is now at hand by eliminating the 2-OH group at the stage of the secondary alcohol, rather than the ketone.